JPH05117168A - Catalytic process for selective alkylation of aromatic hydrocarbon - Google Patents

Abstract

A catalytic process for the selective alkylation of mono- and polycyclic aromatic hydrocarbons is described. The aromatic hydrocarbon is reacted with an alkylating agent in the presence of an acid form of a dealuminated small pore mordenite catalyst having an atomic ratio Si/Al of at least 10:1 to thereby yield the desired alkyl substituted derivative with improved selectivity and improved yield.

Description

Detailed Description of the Invention

The present invention relates to a process for the selective alkylation of aromatic hydrocarbons using a mordenite zeolite type catalyst.

Alkylated aromatic hydrocarbons are valuable products in the chemical industry. In particular, dialkylated monocyclic and polycyclic aromatic hydrocarbon derivatives are of great interest. Many of these compounds are applied in various fields, such as a solvent for a color former for carbonless copying paper and a heat transfer liquid. In addition, dialkylated aromatic hydrocarbon derivatives are a highly demanded class of intermediates because these intermediates can be converted by oxidation to difunctional reagents such as dicarboxylic acids and diols, which have It is of great economic importance for the production of low molecular and high molecular compounds such as monomers, oligomers and polymers esters, amides, carbonates and urethanes. The physicochemical and mechanical properties of these small and high molecular weight compounds depend largely on the type of isomers of the difunctional reagent and the purity or composition of the isomer mixture, which in turn is an intermediate dialkyl derivative of the starting material. Greatly depends on the purity or composition.

An economically convenient method for the preparation of alkylated monocyclic and polycyclic aromatic hydrocarbon derivatives is a catalyst using aromatic hydrocarbon alkenes, alkanols, alkyl halides or any other suitable alkylating agent. Alkylation. Catalytic alkylation processes generally produce a mixture of isomers of alkylated aromatic hydrocarbon derivatives. For a given aromatic hydrocarbon, the type and purity of alkyl isomers or the composition of the isomer mixture will depend on the type of alkylating agent and catalyst and the reaction conditions used in the alkylation process. The pure isomers of dialkyl mono- or polycyclic aromatic derivatives are the most economically attractive ones, but they are difficult due to the difficulty of separating the selected isomers from the isomer mixture by conventional methods. Not easily available. Therefore, there has been an ongoing need for available catalysts that enable the production of selected alkyl-substituted aromatic hydrocarbons with high yield and good selectivity.

It has been found that certain zeolites catalyze the alkylation of aromatic hydrocarbons, and various mordenite zeolites catalyze the alkylation of aromatic hydrocarbons in a more or less selective manner. Is disclosed.

US Pat. No. 3,140,253 and US Pat. No. 3,367,854 use acid-treated mordenite zeolites for the alkylation of monocyclic aromatic hydrocarbons, but the number of grafted alkyl groups and the number of alkyl groups. It is disclosed that there is a limit to the control of the site of chemical conversion.

US Pat. No. 3,251,897 discloses mono- and polycyclic aromatic hydrocarbons of certain crystalline aluminosilicates such as rare earth metal exchanged or proton exchanged X and Y zeolites at 315.5 ° C. ( The use for alkylation at temperatures not exceeding 600 ° F) is described.

Japanese Patent Nos. 56-133224 and 5
8-159427 teaches the use of acid treated mordenite for the gas phase alkylation of benzene and monoalkylbenzenes to p-dialkylbenzenes.

US Pat. No. 4,361,713 discloses various zeolite catalysts treated with halogen-based reactants such as ZSM-5, ZSM-11 and ZSM-12, which are improved paraselections for the alkylation of benzene and toluene. However, it teaches that the conversion rate is insufficient.

EP-A-202 752 describes polycyclic aromatics in which alkylaromatic hydrocarbons are used as alkylating agents in the presence of crystalline mesoporous or macroporous zeolitic acids optionally containing magnesium and / or phosphorus. It teaches the alkylation of hydrocarbons such as naphthalene to β- and / or β, β'-isomers.

US Pat. No. 4,205,189 discloses monoaromatic carbonization using an alkylating agent in the presence of a zeolite having a silica to alumina molar ratio of at least 12 and a constraint index of about 1-12. It teaches the alkylation of hydrogen. The reaction conditions can be adjusted to obtain higher yields of p- or m-isomer, but isomer control is somewhat limited.

US Pat. No. 4,731,497 discloses long chain in the presence of an acid form of zeolite having a pore size of 6.7 to 7.5 Å and a silica / alumina weight ratio of about 30: 1 to 2: 1. It teaches the alkylation of monoalkyl-substituted benzenes with α-olefins. Alkylation occurs in high yield at the para position, and about 70% of the reaction product has a benzene ring attached to the carbon at the 2-position of the α-olefin.

Japanese Patent No. 56-156222 discloses the alkylation of biphenyls using silica-alumina or zeolite catalysts to obtain monoalkylated biphenyl isomer mixtures with a para: meta-isomer ratio of 3: 2. is doing.

US Pat. No. 4,480,142 discloses the alkylation of biphenyls using acid treated montmorillonite to give 2-ethylbiphenyl as the major reaction product.

Japanese Patent Publication 3298 / (1967) discloses a process for the alkylation of aromatic compounds with olefins, alkyl halides or alcohols in the presence of aluminosilicates such as X zeolite, Y zeolite or mordenite. The progress of alkylation of biphenyl results in low conversion and low p, p'-dialkylbiphenyl selectivity.

US Pat. No. 4,283,573 discloses the reaction of a phenolic compound with a reactive derivative having a C ₆ -C ₂₀ alkyl group in the presence of a crystalline zeolite such as mordenite, preferably at the 2-position of the alkyl group. It teaches the formation of p-alkyl-rich derivatives with attached phenol moieties.

EP-A-288 582 teaches the alkylation of aromatic hydrocarbons with olefins, alcohols or alkyl halides in the presence of mordenite zeolite catalysts treated with fluorine containing compounds. It is disclosed that the propylation of biphenyl with propylene selectively proceeds to p, p'-diisopropylbiphenyl in good yield.

EP-A-285 280 is Si
O ₂ / Al ₂ O ₃ molar ratio of selective p biphenyl by lower alkene using 10 or mordenite type catalyst or ZSM-5 zeolite catalyst, discloses p'- alkylation.

US Pat. No. 4,891,448 discloses the alkylation of polycyclic aromatic compounds with alkene reagents in the presence of zeolite catalysts to obtain isomer mixtures enriched in p-alkylated isomers. .. The catalyst used is an acidic mordenite zeolite, the crystal structure of which is a Cmcm symmetric matrix with Cmmm symmetric regions dispersed as measured by X-ray diffraction.

Despite the many methods and numerous catalysts available for the alkylation of aromatic hydrocarbons, the alkylation of aromatic hydrocarbons is run smoothly, in high yield and with high numbers. There remains a need for improved catalytic processes which allow to be carried out with site selectivity.

It is an object of the present invention to provide a catalytic process for the alkylation of aromatic hydrocarbon derivatives into monoalkyl and dialkyl substituted derivatives with high yield and controllable selectivity. Another object of the invention is to provide a catalyst suitable for use in said alkylation process.

[0021]

SUMMARY OF THE INVENTION A Si / Al atomic ratio of at least 10: 1.
It has been found that the acid form of the dealuminized, small pore mordenite of is a particularly useful catalyst in aromatic hydrocarbon alkylation processes. This catalyst combines high alkylation activity with selectivity with respect to the number of alkyl group (s) grafted with the alkylation site. Combining this type of catalyst with appropriately selected reaction conditions results in alkylation to produce isomers at the desired site, and especially with dialkyl-substituted derivatives with improved selectivity from monocyclic and polycyclic aromatic hydrocarbons. It makes it possible to produce in improved yields.

In one embodiment, the present invention provides for the selective alkylation of aromatic hydrocarbons by reacting the aromatic hydrocarbon with an alkylating agent in the presence of a mordenite zeolite catalyst, thereby providing the desired alkyl derivative. With respect to the process, the catalyst in this case is the acid form of dealuminized small pore mordenite with a Si / Al atomic ratio of at least 10: 1.

In another aspect, the present invention provides the acid form of dealuminized small pore mordenite having a Si / Al atomic ratio of at least 10: 1 as a catalyst for the selective alkylation reaction of monocyclic and polycyclic aromatic hydrocarbons. Regarding the use of.

DETAILED DESCRIPTION OF THE INVENTION The aromatic hydrocarbon of the present invention has the formula I (Ar ¹ -X-Ar ² ) _n -Ar ³ (I) (wherein Ar ¹ , Ar ² and Ar ³ are mutually May independently represent an unsubstituted or substituted monocyclic or fused or non-fused polycyclic aromatic group, Ar ³ may also represent hydrogen, X is absent or is an oxygen atom, a sulfur atom , A carbonyl group, a sulfonyl group, or a C ₁ -C ₄ alkylene group, n can be 0 or 1, and when n is 0 Ar ³ is different from hydrogen and (Ar ¹
-X-Ar ² ) _n is hydrogen) and is a monocyclic or polycyclic aromatic hydrocarbon.

Preferably, the monocyclic and / or fused or non-fused polycyclic aromatic groups are phenyl, 1,1'-biphenyl, p-terphenyl, naphthyl, fluorenyl or anthracenyl groups, each group optionally being halogen. A hydroxy group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₄ alkoxycarbonyl group, or a C ₁ -C ₂₀ alkyl group,
Per se halogen, hydroxy, C ₁ -C ₄ alkoxy,
Substituted by one or more substituents selected from those which can be substituted by carboxy or C ₁ -C ₄ alkoxycarbonyl group, and at least one para monocyclic aromatic group - or meta - position, Alternatively, at least one of the corresponding positions of the non-fused or fused polycyclic aromatic group is unsubstituted.

Preferred derivatives of formula I are Ar¹And Ar²Gargling
The gap is also phenyl, and Ar ³Is phenyl, naphth
Tyl or hydrogen, and each phenyl and naphthyl group
Is halogen, hydroxy group, C₁~ C₆Alkoxy group,
Ruboxy group, C₁~ C_FourCarboxyalkyl group, or C₁
~ C₁₂An alkyl group, said group optionally being a halogen
Or hydroxy, carboxy or C₁~ C₆Alkoxy group
1 or 2 independently selected from those substituted by
May be substituted by X groups, X is absent or is
A prime atom, n is 0 or 1, and n is
If 0, Ar³Is different from hydrogen, and (Ar¹-X-A
r²)_nIs a derivative of formula I which is hydrogen.

Preferred aromatic hydrocarbons of formula I are benzene, C ₁ -C ₁₂ alkylbenzenes, biphenyl, mono C ₁
~ C ₁₂ alkylphenylbenzene, p-terphenyl,
Diphenyl ether, 1,4-diphenoxybenzene,
And naphthalene, which are 1 or 2 C _1-
It may or may not be substituted by a C ₁₂ alkyl group.

The most preferred derivative of formula I is biphenyl,
Ethylbenzene, p-terphenyl, naphthalene and diphenyl ether, especially biphenyl.

The alkylating agents of the present invention include C _{2 to} C ₂₀ alkenes, C _{2 to} C ₂₀ polyolefins, C _{4 to} C ₇ cycloalkenes, C _{1 to} C ₂₀ alkanols, C _{1 to} C ₂₀ alkyl halides and C ₁ ~C of ₂₀ alkylaromatic hydrocarbons. Typical alkylating agents are C ₂ -C ₁₂ alkene, C ₁ ~
C ₁₂ alkanols, C ₁ -C ₁₂ alkyl halides and C ₁ -C ₁₂ alkylbenzene derivatives such as ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-
Hexene, 1-octene, 1-decene, 1-dodecene,
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 1-hexanol, 1-octanol, 1 - decanol, 1-dodecanol, and C ₁
-C ₁₂ alkyl chloride, C ₁ -C ₁₂ alkyl bromide, and C ₁ -C _{1 2} alkyl iodide eg methyl chloride, methyl bromide, methyl iodide, ethyl chloride, 1-chloropropane, 2-chloropropane, 2-bromopropane, 1 -Butyl chloride, 2-pentyl chloride, 2-pentyl bromide, 1-hexyl chloride,
2-hexyl chloride, 2-hexyl bromide, 1-octyl chloride, 1-decyl chloride, 1-dodecyl chloride, and diisopropylbenzene.

Preferred alkylating agents are C _{2 to} C ₆ alkenes, C _{1 to} C ₆ alkyl halides and C _{1 to} C ₆ alkanol derivatives. More preferred are C ₃ -C ₄ alkene and C ₃ -C ₄ alkanol derivatives, in particular propene, 1
-Butene, 2-butene, isobutene, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-2-propanol.

The most preferred alkylating agents are propene, isobutene, 2-propanol and 2-butanol, especially propene and 2-propanol.

The essential catalyst used in the alkylation process of the present invention is made from small pore mordenite. Mordenite is generally an aluminosilicate with a SiAl atomic ratio of about 5: 1. Its structure and properties are described in DW Breck, "Zeolite Molecular Sieves" (J. Wiley, 1974), pages 122-124 and 162-163. The crystal structure consists of a series of tetrahedra based on SiO ₄ and AlO ₄ . As a result of its construction, two types of passages are formed, one of which is 2.9x limited by an 8-member ring.
It has a free hole of 5.7 Å,
The second is 6.7 × 7 along the C axis, which is limited by the 12-membered ring.
It has a free angstrom hole. There are two types of mordenites that are distinguished by their adsorption properties, large-pore mordenites adsorb molecules with a kinetic diameter of about 6.6 angstroms, such as benzene, and small-pore mordenites are synthetic as well as natural products. Similarly, it only adsorbs smaller molecules with a kinetic diameter of about 4.4 Å. The diffusion limit present in small-pore mordenite is due to the presence of amorphous material in this channel system, the nature of the cation, and / or the stacking deficiency of crystals in the c-direction of mordenite.
ault) exists. Mordenites are also characterized by differences in morphology, large pore mordenites are generally spherulites, while small pore mordenites are generally rod-shaped.

The characteristics of these small pore mordenites are that F. Raa
tz et al., J. Chem. Soc. Faraday Trans 1, 79, 22.
99-2309 (1983); PC van Geem
Et al., J. Phys. Chem, vol. 92, pp. 1585-1589 (1988), and DW Breck, "Zeolite Molecular Sieves" (J. Wiley, 1974), 1.
It is described on pages 22 to 125.

The catalyst used in the present invention is made from small pore mordenite zeolites which can be made by known methods containing alkali or alkaline earth metal ions or ammonium ions as cations.

The starting small pore mordenite is preferably an alkali metal containing mordenite, most preferably a sodium containing mordenite. The manufacturing method is described, for example, in French Patent No. 1411753. Such starting small pore mordenites are commercially available, for example ZM- sold by La Grande Paroisse, (France).
It is 060 mordenite.

Such preferred mordenites have precisely defined crystallographic properties. Mordenite has a crystalline structure that contains most of the Cmcm symmetric region and substantially no Cmmm symmetric region as measured by conventional X-ray diffraction. The term "majority" means that the crystal structure generally consists of 90% or more, preferably 95% or more and most preferably 99% or more of the region of Cmcm symmetry. The term "substantially free" means that no region of Cmmm is detected in mordenite by conventional X-ray diffraction. This is because the level of possible area of Cmmm symmetry in mordenite is lower than 0.5%,
Most preferably it means lower than 0.01%. The starting material, sodium mordenite, has a symmetry index of 0.7 and is composed mainly of rods.
ates) exist. The rods have an average length of about 50,000 angstroms and an average width of the hexagonal cross section of about 10,000 angstroms, and an average height of about 3,000 angstroms.

Generally, these rods form a mass of about 1 to 1000 microns, typically 1 to 100 microns. The mass size was determined by dispersing mordenite in water using an ultrasonic bath and then using Sympatec Laser Particles.
It was evaluated using Analyzer. X-ray diffraction spectrum of Si
It was made using the emens D-500 instrument, using copper K alpha 1 radiation as a reference.

The unit cell of this mordenite has the elemental formula Na
_{It has 7} Al ₇ Si ₄₀ O ₉₄ · 24 H ₂ O. The Si / Al atomic ratio is 4.5 to 6.5 and is typically close to 6. The sodium level of dry mordenite is 4-6.5% by weight,
It is typically about 5.3% by weight.

Silicon, aluminum and sodium levels were measured by inductively coupled plasma emission spectroscopy using a Philips PV8490 instrument operating at 6000 to 11000 Kelvin temperatures with argon plasma.

The starting small pore mordenite described above does not adsorb significant amounts of benzene or biphenyl. Typically, this mordenite is about 0.01 to 0.02 per gram of mordenite zeolite, calculated on dry mordenite.
It has a sorption capacity for g biphenyl. Biphenyl sorption is carried out by placing mordenite in a helium stream saturated in biphenyl at 200 ° C. until the mordenite is saturated downstream of the sorption vessel as assessed by flame ionization detection of biphenyl in the helium stream.

Mordenites suitable for use as catalysts in the alkylation process of this invention are the acid form of dealuminized small pore mordenite, which is made by the dealuminization of small pore mordenite zeolites.

The dealumination of zeolite is higher than Si /
This is a method of producing a zeolite having an Al atomic ratio.
It is generally achieved by isomorphous replacement of aluminum atoms present in the crystal network, for example by silicon atoms, or by extracting aluminum atoms without their replacement in the crystal skeleton. Isomorphic substitution is accomplished, for example, by exposing mordenite to SiCl ₄ vapor at elevated temperature. By extraction techniques Aluminum can be extracted from the catalyst framework by treatment with mineral or organic acids or with complexing agents. This extraction is typically carried out with sodium or ammonium mordenite. Hydrothermal treatment followed by acid leaching is another method of dealuminizing mordenite, which is commonly done for ammonium mordenite. Yet another method of extracting aluminum atoms from the mordenite skeleton is heat treatment followed by acid leaching, preferably ammonium mordenite.

In general, the dealumination is carried out by subjecting the starting zeolite to one or more treatments of the above-mentioned dealumination process or a combination of the treatments according to the above-mentioned process.

Mordenites suitable for use as the catalyst of the present invention are preferably dealuminized by one or more combined treatments with hot water and acid. These combination treatments are preferably carried out on the small pore mordenite in the ammonium or proton form.

Typically, a catalyst suitable for use in the present invention can be prepared from sodium small pore mordenite by treating it in combination with the following sequence of steps: a. Sodium with ammonium ions or protons. Ion exchange, b. Heat treatment in the presence of steam (hereinafter interchangeably referred to as "steam treatment" or "hot water treatment"), c. Treatment with aqueous acid solution.

Typically, the catalyst is prepared as follows.

A. The sodium ion in the starting material mordenite is converted to mordenite by ionizing ammonium salt, preferably ammonium nitrate or ammonium acetate.
Aqueous solutions of greater than 5 molar concentrations generally from about 20 ° C to about 15 ° C.
Exchange to ammonium ions by treatment at a temperature of 0 ° C.

Optionally, this cation exchange can be repeated with or without an intermediate water wash. Optionally, sodium ion extraction can be carried out by treating the starting material mordenite with a dilute mineral or organic acid.

Generally, the residual sodium content calculated for the dry catalyst is lower than 1% by weight, preferably lower than 0.5% and typically lower than 0.1%.

B. The heat treatment is generally about 300 ° C. in the presence of an atmosphere containing at least about 1% vapor of the ammonium mordenite or proton mordenite obtained in step a.
Performed by heating at a temperature of about 900 ° C. for at least 10 minutes. Preferably 400 for at least 20 minutes in an atmosphere containing at least about 5% mordenite vapor.
Process at a temperature of ℃ -800 ℃. This treatment can also be carried out by the so-called self-steaming method, which consists of calcining mordenite in a limited atmosphere, as well as any other convenient calcination method known in the art. In general, the atmosphere comprises, in addition to steam, conventional gases or gas mixtures known in the art whose constituents have no toxic or undesired effects on mordenite.
Suitable gases and gas mixtures are, for example, nitrogen, helium and air.

During the hydrothermal treatment, the ammonium ions are decomposed to give the proton (acid) form of mordenite.

C. The calcined mordenite from step b. Is then subjected to an acid treatment, which method comprises contacting the mordenite with an aqueous acid solution, preferably an aqueous mineral acid solution.

Preferably, this treatment involves converting mordenite to about 2 parts by weight in a solution of a strong mineral acid with a normality of about 0.1N to 12N.
0 ° C to about 150 ° C, more preferably about 80 ° C to 150 ° C
By stirring at a temperature of at least 10 minutes.

Subsequent drying, typically about 80 ° C to about 1
The mordenite can be washed once or several times with aqueous acid and / or water before it is carried out at 50 ° C.

Optionally, the heat treatment in the presence of steam and the subsequent acid treatment can be repeated once or several times. Optionally, after the final acid treatment, a heat treatment without addition of steam is typically carried out at a temperature of about 400 ° C to about 700 ° C.

As a result of the hydrothermal treatment, aluminum atoms are released from the crystalline framework of the catalyst and are generally deposited in the porous system. During the subsequent acid treatment most of the aluminum species dissolve and are removed from the catalyst. The amount of aluminum species removed by the combination of hot water and acid treatment is generally greater than 50%, preferably greater than 80% of the total aluminum content,
More preferably, it is more than 90%. The degree of aluminum species removal can be controlled by the dealuminizing conditions. This dealuminizing treatment brings the Si / Al atomic ratio close to 6 from its typical original value of at least 10: 1 Si / Al.
Increase atomic ratio. The mordenite used in the present invention is generally 20: 1 to 1000: 1, preferably 30: 1 to
200: 1, more preferably 60: 1 to 150: 1, and most preferably 80: 1 to 120: 1 Si / Al.
It has an atomic ratio.

The Si / Al atomic ratio is a comprehensive ratio based on the total amount of silicon and aluminum in mordenite (bone nucleus plus extrabone nucleus), and the Si / Al atomic ratio of the crystal matrix (bone nucleus) is significantly different. May
And it should be understood that ratios higher than 1000: 1 can be reached.

The porosity of the small pore mordenite catalyst during dealuminization by the above-described combination treatment changes significantly. After removing about 20% of the aluminum atoms from the crystal skeleton by the combined treatment of steam and acid, the porous system is unblocked and larger molecules, such as biphenyl, are sorbed on the catalytic porous system. You can About 6.
The obstruction of this porous system allowing free diffusion of molecules with a kinetic diameter of 6 Å, eg biphenyl, is a manifestation of the changes that occur in the porous system.

Porous systems of small-pore mordenite are generally microporous (radius of about 3 to 15 angstroms), medium-pore (about 15).
~ 1000 angstrom radius) and giant holes (10
Radius of greater than or equal to 00 Å).

The removal of obstacles also creates new pores, which is indicated by an increase in the volume of mesopores and macropores after the combined treatment of the starting sodium pore mordenite.

Typically, the biphenyl adsorption is increased as a result of the combined treatment of hot water and acid, from about 0.016 g / g mordenite to 0.05 to 0.12 g / g mordenite calculated on the dry catalyst. You can Measurement of pore volume may be accomplished by methods known in the art, such as S. L.
Owell, "A Guide to Powder Surface Area" (J. Wiley, 197).
9 years). Typically, the acid form of the dealuminized small pore mordenite suitable for use in the present invention is a porous system of mordenite zeolite such that the ratio of mesopore to macropore system to the total pore system is 0.2 to 0.5. have.

The characteristics of the typical mordenite catalyst used in the present invention are as follows. That is, in acid form, ie, substantially all cations are protons, about 20:
Si / Al atomic ratio of 1 to about 200 to 1, about 0.7 to about 2.
A symmetry index of 6, calculated on a dry basis of about 0.05 to about 0.12 g biphenyl sorption capacity per gram of catalyst, the ratio of medium pore size to macropore volume to total pore volume of 0.2 to 0. Cm which is substantially Cmmm and has no symmetry
The appearance is in the form of an agglomerate composed of a rod-shaped crystal structure, which is a cm-symmetric matrix.

The symmetry index was obtained from the X-ray diffraction spectrum of the mordenite zeolite. It is (111) and (24
1) Defined as the quotient of the sum of the reflection peak heights divided by the (350) reflection peak heights. Typically 0.5 to 0.8 for the starting small pore mordenite, and typically 0.7 to 2.6 after the above-described dealumination treatment.

Pore sodium, ammonium or proton mordenite, optionally before or after steaming or acid treatment, may be reduced in size using methods known in the art, such as crossed air jet milling. can do. In the production of the catalyst used in the examples described below, this operation was performed using AlpineAe
Performed using a roplex 200 AFG instrument. The size of the reduced size catalyst generally ranges from about 0.1 to about 1000 microns, and typically ranges from about 0.1 to about 100 microns. The most preferred size is 0.1-10 microns.

The mordenite is directly in a suitable form known in the art as the catalyst of the present invention, eg in powder form,
Alternatively, it can be used in the form of powder, extrudate, pellets, tablets, granules, spheres or the like, with or without combination with a suitable support and / or binder known in the art. Such supports and binder materials may be inert or have an inherent catalytic activity compatible with that of the mordenite catalyst. Examples of such materials are oxides such as alumina, silica, magnesia and silica-alumina; activated carbon, diatomaceous earth, and various clays. The catalyst form used in the alkylation process of the present invention can be prepared by techniques well known in the art.

In the alkylation process of the present invention, virtually any weight ratio of catalyst to aromatic hydrocarbons can be used, but is practically limited by the conversion rate, which is unacceptable. Don't be late. The catalyst: aromatic hydrocarbon weight ratio is generally about 1:
1000-1: 0.1, preferably 1: 500-1:
1, more preferably 2: 100 to 1:10, most preferably about 5: 100.

Alkylating agent: The ratio of aromatic hydrocarbon depends on the number of alkyl groups grafted to the aromatic hydrocarbon, the nature of the alkylating agent and the aromatic hydrocarbon, the catalyst and the reaction conditions such as temperature, pressure, reaction time. And can be changed depending on the type of the reactor. Generally, however, the molar ratio of alkylating agent to aromatic hydrocarbon will be 0.5 to 5, typically 0.7 to 2, and preferably about 1: 1 per alkyl group grafted to the aromatic hydrocarbon. keep.

The alkylation process of the present invention can be carried out in batch or continuous alkylation reactors known in the art such as fixed bed, slurry or fluid bed reactors, countercurrent reactors and the like. Alkylation can be carried out in the liquid or gas phase using alkylating agents and / or aromatic hydrocarbons, or the aromatic hydrocarbons or alkylating agents can act as a solvent for the other. ,
Alternatively, it is possible to use a solvent which remains inert under the reaction conditions. Further, the aromatic hydrocarbon can be brought into contact with the required amount of alkylating agent at once at the start of the reaction or gradually with the progress of the reaction.

The optimum reaction temperature and pressure will depend on the other reaction conditions, the nature of the aromatic hydrocarbon and the alkylating agent, as well as the nature of the desired reaction product. Typically the reaction temperature is about 1
00 ° C to about 400 ° C, preferably about 150 ° C to about 300
Keep at ℃.

Alkylation processes generally range from about 1 kPa to about 40 kPa.
It can be carried out under a pressure of 00 kPa, typically about 10 kPa to about 1000 kPa, preferably about 10 kPa to about 500 kPa.

The optimum time for contacting the aromatic hydrocarbon with the alkylating agent in the presence of the catalyst depends on the nature of the aromatic hydrocarbon,
It largely depends on the alkylating agent, catalyst, type of reactor, reaction conditions and desired reaction product. The reaction time can vary widely from a few seconds to a few hours. The optimum reaction time can be easily determined by those skilled in the art.

The product obtained by the process of the present invention comprises a mixture of alkylated monocyclic or polycyclic aromatic hydrocarbons of different isomers, the distribution of the alkylated isomers of which, depending on the selection of the appropriate reaction conditions, It is possible to control and regulate towards higher levels of the desired para- or linear isomer as well as towards higher levels of the meta- or kinked isomer.

Para- or linear alkylated isomers are those in which the alkyl group (s) is attached to the end of the aromatic hydrocarbon molecule to yield a product with the smallest critical diameter. Meta- or kink isomers are those in which at least one alkyl group is attached to the aromatic hydrocarbon in the meta-position or equivalent positions. The latter molecule has a large critical diameter compared to para- or linear alkylated isomers. In the case of alkylation of biphenyl, for example, the p-alkylation product is p, p'-diisopropylbiphenyl and the m-alkylation product is m, p-diisopropylbiphenyl. In the case of alkylation of naphthalene, for example, the linear alkylation product is 8,6-diisopropylnaphthalene and the kink alkylation product is 2,7-diisopropylnaphthalene.

Detailed Description of the Invention

For a given aromatic hydrocarbon, the appropriate reaction conditions for optimal production of the selected alkylated aromatic hydrocarbon isomer or isomer mixture are selected by standard methods in the art. The selection can be performed, for example, by evaluating the change in the composition of the reaction product (eg, gas chromatography (G
C) or analyzed by GC-mass spectrometry), this evaluation being obtained by experiments in which one or more reaction parameters such as temperature and pressure are varied. Examples 4-19 below are isomers with a selected distribution of alkylated isomers /
It demonstrates that the isomer mixture can be controlled and regulated.

In the process for alkylating biphenyls using propylene according to the present invention, when the other reaction conditions are substantially the same, for example, the desired reaction product is p, p'-
In the case of diisopropyl 1,1'-biphenyl, the reaction temperature was maintained at 175-220 ° C and the desired product was m,
In case of p'-diisopropyl / 1,1'-biphenyl 2
Most preferably, the temperature is maintained at 20 ° C to 275 ° C.

For the purposes of this invention, alkylation of aromatic hydrocarbons to the selective isomers includes conversion of the starting hydrocarbons, selectivity to the desired isomer and the isomerization obtained in the crude alkylation product. The body yield is more suitable. The conversion rate represents the mol% of the starting aromatic hydrocarbon converted in the alkylation reaction.

In the alkylation of the present invention, the conversion will vary over a very wide range depending on the aromatic hydrocarbon, the alkylating agent, the reaction temperature and pressure, the catalyst product, and the mode of operation such as continuous or batch operation. Conversion of at least 5%, typically at least 30 for batch operations
%, Preferably at least 50% and most preferably at least 70%.

The selectivity to a given alkylated isomer is also expressed in mol% of the starting aromatic hydrocarbon converted to the desired isomer.
Is. The selectivity can be expressed on the basis of the product group, for example as mol% of a particular dialkylated isomer with respect to the total amount of dialkylated isomers formed. In the reaction of biphenyl with propene, the crude reaction product is rich in p, p'-dialkyl isomers depending on the reaction conditions and the catalyst.
Or rich in m, p'-dialkyl isomers, or m, p '
And alkylates enriched in a mixture of m and m'-dialkyl isomers. Typically, in the process of the present invention, the selectivity to one particular dialkyl isomer in the dialkylated biphenyl group is from about 20 mol% to about 90 mol%.

In the process of the present invention, the selectivity to a particular dialkylated isomer based on the group of dialkylated products is at least 20 mol%, preferably at least 30 mol%,
Most preferably it is at least 50 mol%. The yield of any particular isomer in a crude alkylated aromatic hydrocarbon represents the product of the conversion and selectivity numbers.

The following examples are illustrative of the catalysts and methods of this invention and should not be construed as limiting its scope. All percentages are mol% unless otherwise noted
It is represented by. Unless otherwise stated, the term "addition pressure" means the pressure of the alkylating agent added at the beginning of the reaction relative to the pressure of the reaction mixture at the set reaction temperature. "Additional pressure"
The value of is maintained throughout the reaction temperature. The starting mordenites are small pore sodium or ammonium mordenites, respectively ZM by La Grande Paroisse, France.
Manufactured as -060 and ZM-101.

Examples 22-26 and 29-31 are comparative examples and demonstrate the unique catalytic properties of the catalysts of this invention.
These examples show that when the acid form of small pore mordenite that is not dealuminated is used as a catalyst, the alkylation process of aromatic hydrocarbons proceeds poorly or not at all, and the dealuminated as-manufactured steam ( It illustrates that the reaction proceeds with low selectivity and yield when using the acid form of dealuminized small pore mordenite carried out without hydrothermal treatment).

Example 1: Preparation of catalyst ZM-060 small pore sodium mordenite is converted to ammonium form by treatment with an aqueous solution of ammonium nitrate as follows: 400 g sodium mordenite 10
Contact with 1 liter of an aqueous solution containing 0 g of ammonium nitrate. The mixture is stirred at 60 ° C. for 4 hours. The ammonium mordenite formed is collected by filtration and washed with deionized water until a pH of 7 is reached. Ammonium mordenite is hydrothermally treated at normal pressure in a horizontal furnace passing an air stream at a rate of 250 Nl / hr. The temperature is gradually increased to 680 ° C at a rate of 150 ° C / hour. Steam is introduced into the air from about 300 ° C. Saturator level of steam (saturato
Adjust using r). The water flow is around 80 g / hour. After 5 hours at 680 ° C. under these conditions, the furnace heating is stopped and the steam flow is stopped at 300 ° C. The mordenite is then treated with a 6N aqueous nitric acid solution at 90 ° C. for 3 hours with vigorous stirring. The catalyst is filtered off and washed twice with 70 ° C. deionized water. Finally the solid is dried at 150 ° C. for 10 hours. Analysis of the catalyst gives the following results.

Si / Al atomic ratio: 100: 1 Total pore volume: 0.328 ml / g Symmetric index: 1.68 Ratio of medium porosity to macroporosity to total porosity: 0.33

Example 2: Preparation of catalyst ZM-060 small pore mordenite is converted to the ammonium form by treatment with an aqueous solution of ammonium nitrate as described in Example 1.

Next, ammonium mordenite was added at 560 ° C.
It is heated to room temperature and subjected to hot water treatment under normal pressure in a horizontal rotating tubular furnace operated on a continuous basis. Ammonium mordenite is continuously fed to the rotary furnace and brought into contact with steam at this elevated temperature.
The furnace operation is adjusted to give the mordenite a residence time of 1 hour in the high temperature range. 80g water measured at 25 ℃
/ Feed to the furnace at a rate corresponding to an hour. Then, mordenite was put in a static furnace at 250N under normal pressure.
Work with a stream of air at a rate of 1 liter / hour.
The temperature is gradually increased from 680 ° C to 700 ° C at a rate of 150 ° C / hour. Steam is introduced into the air from about 300 ° C.
Adjust the level with a saturator. The water flow is around 80 g / hour. After 4 hours at 680 ° C to 700 ° C under these conditions, the furnace heating is stopped and the steam flow is stopped at 300 ° C. Then mordenite at 6 ° C at 6N
Treat with aqueous nitric acid for 3 hours with vigorous stirring. The catalyst is filtered off and recovered with deionized water at 70 ° C.
Wash once with 60 ° C. 1N aqueous nitric acid solution and finally with 70 ° C. deionized water. The mordenite is then dried at 150 ° C for 10 hours. Analysis of the catalyst gives the following results.

Si / Al atomic ratio: 80: 1 Total pore volume: 0.257 ml / g Symmetric index: 1.63 Ratio of medium porosity to macroporosity to total porosity: 0.35

Example 3 Preparation of Catalyst ZM-060 small pore sodium mordenite 5.10 ⁵
Alpine Aeroplex 200 operated at Pa pressure and room temperature
Supply to AGF equipment at a throughput of about 4 kg / hour. The particle sorter is run at about 11000 rpm to obtain a mordenite size of about 0.9-6 microns. This reduced size mordenite was first subjected to ammonium exchange as described in Example 1 and then first hydrothermally treated at 620 ° C. in a horizontal rotary tube furnace as described in Example 2 and then acid treated. To do. The mordenite was then treated with 6 as described in Example 2.
A second hot water treatment at 80-700 ° C., followed by a second acid treatment and a final drying step. Analysis of the catalyst gives the following results.

Si / Al atomic ratio: 90: 1 Total pore volume: 0.303 ml / g Symmetry index: 1.61 Ratio of medium porosity to macroporosity to total porosity: 0.40

Example 4: Alkylation of ethylbenzene-paraselectivity Ethylbenzene (700 g) and the catalyst from Example 1 (3
5 g or 5% by weight with respect to ethylbenzene) 1 in a 2 liter / pressure autoclave operated with stirring
Contact with propylene for 2 hours at a temperature of 60 ° C. and a propylene addition pressure of 0.8 × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography gives a conversion of 79.6%, a yield of m-isopropylethylbenzene of 20.6%, a yield of p-isopropylethylbenzene of 54.5%. The sum of monoisopropylethylbenzene isomers represents 95.4% of the total conversion. The selectivity to p-isopropylethylbenzene is 68.5% and the selectivity to m-isopropylethylbenzene is 25.9%.

Example 5 Alkylation of Ethylbenzene-Metaselectivity Ethylbenzene (700 g) and catalyst from Example 2 (3
5 g or 5% by weight with respect to ethylbenzene) in a 2 l / pressure autoclave operated with stirring 2
It is contacted with propylene at a temperature of 50 ° C. and a propylene addition pressure of 0.3 × 10 ⁵ Pa for 5 hours. Analysis of the reaction mixture by gas chromatography gives a conversion of 95.1%, a yield of m-isopropylethylbenzene of 49.7%, a yield of p-isopropylethylbenzene of 33.1%. The sum of monoisopropylethylbenzene isomers represents 88.3% of the total conversion. The selectivity to p-isopropylethylbenzene is 34.8% and the selectivity to m-isopropylethylbenzene is 52.3%.

Example 6: Alkylation of 1,1'-biphenyl-paraselectivity: 1,1'-biphenyl (80 g) and the catalyst from Example 3 (4 g or 5% by weight of biphenyl) run with stirring. The propylene is contacted with propylene at a temperature of 250 ° C. at a propylene addition pressure of 1 × 10 ⁵ Pa for 6 hours. Analysis of the reaction mixture by gas chromatography gave a conversion of 93.5%, a p of 65%,
A yield of p'-diisopropylbiphenyl and a yield of m, p'-diisopropylbiphenyl of 12.7% are obtained. The sum of diisopropylbiphenyl products represents 84.2% of the total conversion. The selectivity to p, p'-diisopropylbiphenyl is 69.5% and the selectivity to m, p'-diisopropylbiphenyl is 13.6%.

Example 7: Alkylation of 1,1'-biphenyl-paraselectivity 1,1'-biphenyl (800 g) and catalyst from Example 1 (40 g or 5% by weight of biphenyl) run with stirring. 2 liters / pressure 200 in autoclave
Contact with propylene for 6 hours at a propylene addition pressure of 0.8 × 10 ⁵ Pa at a temperature of ° C. 62.4% conversion by analysis of the reaction mixture by gas chromatography,
A yield of p, p'-diisopropylbiphenyl of 34.2% and a yield of m, p'-diisopropylbiphenyl of 6.7% are obtained. The sum of the diisopropyl biphenyl products represents 66.1% of the total conversion. The selectivity to p, p'-diisopropylbiphenyl is 54.7% and the selectivity to m, p'-diisopropylbiphenyl is 10.7%.

Example 8: Alkylation of 1,1'-biphenyl-paraselectivity: 1,1'-biphenyl (800 g) and the catalyst from Example 1 (40 g or 5% by weight of biphenyl) are run with stirring. 2 liters / pressure 250 in autoclave
℃ of contacting a 5 hour propylene propylene added pressure temperature 7 × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography gave a conversion of 87.0%, 40.
5% yield of p, p'-diisopropylbiphenyl, 2
A yield of m, p'-diisopropylbiphenyl of 0.2% is obtained. The sum of the diisopropyl biphenyl products represents 72.7% of the total conversion. The selectivity to p, p'-diisopropylbiphenyl is 46.6% and the selectivity to m, p'-diisopropylbiphenyl is 23.2%.

Example 9: Alkylation of 1,1'-biphenyl-paraselectivity 200 mg of the catalyst from Example 1 was introduced into a glass microreactor placed in an oven at 200 ° C. The catalyst bed is contacted at 200 ° C. with a stream of helium containing 1,6.10 ³ Pa of 1,1′-biphenyl and 4.10 ⁴ Pa of propylene. The total flow rate of the gas mixture was 36 ml / min and the biphenyl W.S. H. S. V. (Weight space-time velocity)
Is 1.2 g of biphenyl / hour / g of catalyst. Gas chromatographic analysis of the reaction mixture after 70 minutes was 36.
A conversion of 7%, a yield of p, p'-diisopropylbiphenyl of 20.5% and a yield of m, p'-diisopropylbiphenyl of 3.3% are shown. The sum of the diisopropyl biphenyl products represents 66.5% of the total biphenyl conversion. p,
Selectivity to p'-diisopropylbiphenyl is 55.8.
% And the selectivity to m, p'-diisopropylbiphenyl is 9.0%.

Example 10: Alkylation of 1,1'-biphenyl-metaselectivity: 1,1'-biphenyl (800 g) and the catalyst from Example 1 (40 g or 5% by weight of biphenyl) run with stirring. 2 liters / pressure 250 in autoclave
Contact with propylene for 6 hours at a propylene addition pressure of 0.8 × 10 ⁵ Pa at a temperature of ° C. Analysis of the reaction mixture by gas chromatography gives a conversion of 93.6%,
A yield of 11.4% of p, p'-diisopropylbiphenyl, a yield of 35.4% of m, p'-diisopropylbiphenyl and a yield of 8.0% of m, m'-diisopropylbiphenyl are obtained. .. The sum of the diisopropylbiphenyl products represents 59.8% of the total conversion. The selectivity to p, p'-diisopropylbiphenyl is 12.2% and the selectivity to m, p'-diisopropylbiphenyl is 37.8% and m,
Conversion rate to m'-diisopropylbiphenyl is 8.5%
Is.

Example 11: Alkylation of 1,1'-biphenyl-metaselectivity: 1,1'-biphenyl (800 g) and the catalyst from Example 1 (40 g or 5% by weight of biphenyl) run with stirring. 2 liters / pressure 275 in pressure autoclave
Contact with propylene for 6 hours at a propylene addition pressure of 0.2 × 10 ⁵ Pa at a temperature of ° C. Analysis of the reaction mixture by gas chromatography gives a conversion of 94.1%,
Yield of p, p'-diisopropylbiphenyl of 8.2%,
A yield of m, p'-diisopropylbiphenyl of 26.9% and a yield of m, m'-diisopropylbiphenyl of 17.1% are obtained. The sum of the diisopropyl biphenyl products represents 57.4% of the total conversion. The selectivity to p, p'-diisopropylbiphenyl is 8.7% and the selectivity to m, p'-diisopropylbiphenyl is 28.6% and m, m '.
-The conversion to diisopropyl biphenyl is 18.2%.

Example 12: Alkylation of 1,1'-biphenyl-metaselectivity: 1,1'-biphenyl (800 g) and the catalyst from Example 1 (40 g or 5% by weight of biphenyl) run with stirring. 2 liters / pressure 200 in autoclave
Contact with propylene for 5 hours at a propylene addition pressure of 0.2 × 10 ⁵ Pa at a temperature of ° C. Analysis of the reaction mixture by gas chromatography gave a conversion of 92.2%,
A yield of p, p'-diisopropylbiphenyl of 11.3%, a yield of m, p'-diisopropylbiphenyl of 32.0% and a yield of m, m'-diisopropylbiphenyl of 11.0% are obtained. .. The sum of diisopropylbiphenyl products represents 60.0% of the total conversion. Selectivity to p, p'-diisopropylbiphenyl is 12.3%, m, p'-
The selectivity to diisopropylbiphenyl is 34.6% and the conversion to m, m'-diisopropylbiphenyl is 11.
9%.

Example 13: Alkylation of 1,1'-biphenyl-metaselectivity 200 mg of the catalyst from Example 1 were introduced into a glass microreactor placed in an oven at 200 ° C. The catalyst bed is contacted at 200 ° C. with a stream of helium containing 1,6.10 ³ Pa of 1,1′-biphenyl and 8.10 ³ Pa of isopropanol. The total flow rate of the gaseous mixture was 36 ml / min and the biphenyl W.S. H. S. V. The (weight hourly space velocity) is 1.2 g of biphenyl / hour / g of catalyst. Gas chromatographic analysis of the reaction mixture after 70 minutes showed a conversion of 59.3%, a yield of p, p'-diisopropylbiphenyl of 9.8%, a yield of m, p'-diisopropylbiphenyl of 26.4%. And the yield of m, m'-diisopropylbiphenyl of 5.3%. The sum of the diisopropyl biphenyl products represents 70% of the total biphenyl conversion. The selectivity to p, p'-diisopropylbiphenyl is 16.5%, the selectivity to m, p'-diisopropylbiphenyl is 44.5%, and the selectivity to m, m'-diisopropylbiphenyl is Is 8.9%.

Example 14 Alkylation of diphenyl ether-paraselectivity 225 ° C. in a 2 liter / pressure autoclave operated with stirring diphenyl ether (800 g) and the catalyst from Example 1 (40 g or 5% by weight of diphenyl ether). The propylene is contacted with the propylene at the temperature of 1 × 10 ⁵ Pa and the addition pressure of propylene for 5 hours. Analysis of the reaction mixture by gas chromatography showed a conversion of 76.6%,
The yield of p, p'-diisopropyldiphenyl ether of 35.3% and the yield of m, p'-diisopropyldiphenyl ether of 16.5% are shown. The sum of the diisopropyl diphenyl ether products represents 69.6% of total conversion.
The selectivity to p, p'-diisopropyldiphenyl ether is 46.0% and the selectivity to m, p'-diisopropyldiphenyl ether is 21.5%.

Example 15: Alkylation of diphenyl ether-metaselectivity 25 In a 300 ml / pressure autoclave operated with stirring diphenyl ether (80 g) and the catalyst from Example 1 (4 g or 5% by weight of diphenyl ether).
It is contacted with propylene at a temperature of 0 ° C. and an addition pressure of propylene of 0.8 × 10 ⁵ Pa for 5 hours. Analysis of the reaction mixture by gas chromatography showed a conversion of 92.4%,
The yield of p, p'-diisopropyldiphenyl ether of 27.5% and the yield of m, p'-diisopropyldiphenyl ether of 36.0% are shown. The sum of the diisopropyl diphenyl ether products represents 74.8% of conversion. p,
The selectivity to p'-diisopropyldiphenyl ether is 29.7% and the selectivity to m, p'-diisopropyldiphenyl ether is 39.0%.

Example 16 Alkylation of Naphthalene-Linear Selectivity Naphthalene (80 g) and catalyst from Example 1 (4 g or 5% by weight of naphthalene) are run with stirring 30.
0 ml / pressure 0.8 at a temperature of 220 ° C. in an autoclave
It is contacted with propylene for 3 hours at an addition pressure of propylene of × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography showed 89.0% conversion, 34.4% 2,6-.
Yield of diisopropylnaphthalene, and 11.8% of 2,
The yield of 7-diisopropylnaphthalene is shown. The sum of diisopropylnaphthalene represents 51.7% of conversion.
The selectivity to 2,6-diisopropylnaphthalene is 38.7.
%, And the selectivity to 2,7-diisopropylnaphthalene is 13.3%.

Example 17: Alkylation of Naphthalene-Kink Selectivity Naphthalene (800 g) and catalyst from Example 2 (40 g).
Or 5% by weight of naphthalene) in a 2 liter / pressure autoclave operated with stirring at a temperature of 250 ° C. and an addition pressure of propylene of 0.8 × 10 ⁵ Pa for 1 hour 3
Contact with propylene for 0 minutes. Analysis of the reaction mixture by gas chromatography gave a conversion of 82.3%, 15.0.
% 2,6-diisopropylnaphthalene yield, and 9.
The yield of 4% 2,7-diisopropylnaphthalene is shown. The sum of diisopropylnaphthalene is 32.
Indicates 5%. The selectivity to 2,6-diisopropylnaphthalene is 18.2% and the selectivity to 2,7-diisopropylnaphthalene is 11.5%.

Example 18: Alkylation of 1,1'-biphenyl-paraselectivity The biphenyl (80 g) and the catalyst from Example 1 (4 g or 5% by weight of biphenyl) are run with stirring 30.
0 ml / pressure 1.1 in autoclave at a temperature of 225 ° C
It is contacted with 1-butene for 8 hours at an added pressure of 1-butene of × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography showed a conversion of 79.7% and a p, p 'of 43.9%.
-Yield of diisobutylbiphenyl, 6.8% m, p'-
The yield of diisobutylbiphenyl is shown. The sum of diisobutylbiphenyl represents 64.3% of the total conversion. p, p '
The selectivity to diisobutylbiphenyl is 55.0% and the selectivity to m, p'-diisobutylbiphenyl is 8.5%.

Example 19: Alkylation of 1,1'-biphenyl-metaselectivity Biphenyl (80 g) and the catalyst from Example 1 (4 g or 5% by weight of biphenyl) are run with stirring 30.
0 ml / pressure 1.1 in an autoclave at a temperature of 250 ° C.
It is contacted with 1-butene for 7 hours at an added pressure of 1-butene of × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography showed conversion of 86.9%, p, p 'of 17.9%.
-Yield of diisobutylbiphenyl, 19.4% m, p '
-Indicates the yield of diisobutylbiphenyl. The sum of diisobutylbiphenyl represents 45.2% of the total conversion. p,
Selectivity to p'-diisobutylbiphenyl is 20.6%
And the selectivity to m, p'-diisobutylbiphenyl is 22.3%.

Example 20: Preparation of catalyst ZM-060 small pore sodium mordenite is treated with ammonium nitrate as in Example 1 to replace sodium with ammonium. The catalyst was dealuminized by hot water treatment in the presence of steam as in Example 1, this treatment being 62
Perform at 0 ° C. for 5 hours. After cooling, the catalyst is treated with a 6N aqueous nitric acid solution at 90 ° C. for 3 hours with vigorous stirring. The catalyst is filtered off and washed twice with 70 ° C. deionized water. Finally the solid is dried at 150 ° C. for 10 hours. Analysis of the catalyst gives the following results.

Si / Al atomic ratio: 50: 1 Symmetric index: 1.85 Total pore volume: 0.32 ml / g Ratio of medium to large pores to total porosity: 0.422

Example 21: Preparation of catalyst The catalyst from Example 20 is further dealuminized by a hydrothermal treatment carried out in the presence of steam as in Example 1, this treatment being carried out at 700 ° C. for 5 hours. After cooling, the catalyst was heated to 110 ° C
Treat with an aqueous solution of N-nitric acid for 4 hours with vigorous stirring. The catalyst is filtered off and washed twice with 70 ° C. deionized water. Finally the solid is dried at 150 ° C. for 10 hours. Analysis of the catalyst gives the following results.

Si / Al atomic ratio: 150: 1 Symmetric index: 2.18 Total pore volume: 0.31 ml / g Ratio of medium pores to macropores to total porosity: 0.45

Comparative Example 22: Preparation of catalyst ZM-060 small pore sodium mordenite is converted to the acid form by treating with 1N aqueous hydrochloric acid solution as follows: 20 g small pore sodium mordenite is converted to 200 ml 1N.
Contact with aqueous hydrochloric acid for 30 minutes at room temperature with vigorous stirring. The hydrogen mordenite formed is collected by filtration,
Rinse to pH 7 with deionized water. The recovered solid is air dried at 100 ° C., heated in a stream of air at 700 ° C. for 2 hours, then cooled to room temperature. The mordenite is treated with a 6N aqueous nitric acid solution under reflux for 2 hours with vigorous stirring. The catalyst is collected by filtration and washed with deionized water until pH7. Analysis of the catalyst gives the following results.

Si / Al atomic ratio: 10: 1 Symmetric index: 1.58 Total pore volume: 0.216 ml / g Medium pore to macroporosity ratio: 0.18 The catalyst before use was in air at 700 ° C. Heat for 2 hours to activate.

Comparative Example 23: Preparation of catalyst ZM-101 small pore ammonium mordenite was added at 700 ° C.
In a stream of air for 2 hours and then cooled to room temperature. The mordenite is treated with a 6N aqueous nitric acid solution under reflux for 2 hours with vigorous stirring. The catalyst is collected by filtration and washed with deionized water until pH7. Analysis of the catalyst gives the following results.

Si / Al atomic ratio: 20: 1 Symmetric index: 1.56 Total pore volume: 0.285 ml / g Ratio of medium pores to macroporosity to total porosity: 0.42 In air for 2 hours.

Comparative Example 24: Alkylation of 1,1'-biphenyl Biphenyl (80 g) and the catalyst from Comparative Example 22 (1.6
g or 2% by weight of biphenyl) is contacted with propylene for 4 hours at a temperature of 250 ° C. and a total pressure of 8.2 × 10 ⁵ Pa in a 300 ml / pressure autoclave operated with stirring. Analysis of the reaction mixture by gas chromatography shows a conversion of 2.15% and a yield of p, p'-diisopropylbiphenyl of 0.1%. The sum of the diisopropyl biphenyl derivatives represents 7.3% of the total conversion. p,
The selectivity to p'-diisopropylbiphenyl is 5.48.
%.

Comparative Example 25: Alkylation of 1,1′-biphenyl Biphenyl (80 g) and catalyst from Comparative Example 23 (1.6
g or 2% by weight of biphenyl) is contacted with propylene for 4 hours at a temperature of 250 ° C. and a total pressure of 8.2 × 10 ⁵ Pa in a 300 ml / pressure autoclave operated with stirring. Analysis of the reaction mixture by gas chromatography shows a conversion of 36.0% and a yield of p, p'-diisopropylbiphenyl of 4.9%, a yield of m, p'-diisopropylbiphenyl of 0.7%. .. The sum of the diisopropylbiphenyl derivatives represents 16.6% of the total conversion. p,
Selectivity to p'-diisopropylbiphenyl is 13.7
%, And the selectivity to m, p'-diisopropylbiphenyl is 2.1%.

Comparative Example 26: Alkylation of 1,1′-biphenyl Biphenyl (80 g) and catalyst from Comparative Example 22 (4 g or 5% by weight of biphenyl) are run with stirring 30
0 ml / pressure 5 × 1 at a temperature of 250 ° C. in an autoclave
Contact with propylene for 4 hours at a pressure of addition of propylene of 0 ⁵ Pa. Analysis of the reaction mixture by gas chromatography shows a conversion of 5.6% and a yield of p, p'-diisopropylbiphenyl of 0.2%. The sum of diisopropylbiphenyl represents 4.7% of the total conversion. p, p'-
The selectivity to diisopropylbiphenyl is 3.5%.

Example 27: Alkylation of 1,1′-biphenyl Biphenyl (80 g) and catalyst from Example 20 (4 g or 5% by weight of biphenyl) are run with stirring 3
00 ml / pressure in an autoclave at a temperature of 200 ° C.
Contact with propylene for 4 hours at an addition pressure of propylene of 8 × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography showed a conversion of 33.4%, a p of 12.0%,
Yield of p'-diisopropylbiphenyl, 1.3% of m,
The yield of p'-diisopropylbiphenyl is shown. The sum of diisopropylbiphenyl represents 40.8% of all conversions. The selectivity to p, p'-diisopropylbiphenyl is 35.9% and the selectivity to m, p'-diisopropylbiphenyl is 3.9%.

Example 28: Alkylation of 1,1′-biphenyl Biphenyl (80 g) and the catalyst from Example 21 (4 g or 5% by weight of biphenyl) are run with stirring 30
0 ml / pressure 0.8 at a temperature of 200 ° C. in an autoclave
It is contacted with propylene for 4 hours at an addition pressure of propylene of × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography shows a conversion of 8.0%, a yield of p, p'-diisopropylbiphenyl of 1.3%, a yield of m, p'-diisopropylbiphenyl of 0.1%. .. The sum of diisopropylbiphenyl represents 18.5% of the total conversion. p,
Selectivity to p'-diisopropylbiphenyl is 16.2
%, And the selectivity to m, p'-diisopropylbiphenyl is 1.7%.

Comparative Example 29: Preparation of Catalyst 150 ZM-101 small pore ammonium mordenite with Si / Al atomic ratio of 5.8: 1 was run in a static furnace through a stream of air.
Heat for 4 hours while gradually raising the temperature to 600 ° C at a rate of ° C / hour. Analysis of the solid obtained after cooling indicates that the catalyst is in acid form.

Comparative Example 30: Alkylation of 1,1′-biphenyl Biphenyl (80 g) and catalyst from Comparative Example 29 (4 g or 5% by weight of biphenyl) are run with stirring 3
00 ml / pressure in an autoclave at a temperature of 200 ° C.
Contact with propylene for 5 hours at an addition pressure of propylene of 8 × 10 ⁵ Pa. Analysis of the reaction mixture by gas chromatography showed 0.4% conversion, 0.02% m, p '.
Yield of diisopropylbiphenyl and p, 0.5%,
The yield of p'-diisopropylbiphenyl is shown.

Comparative Example 31: Alkylation of 1,1′-biphenyl 200 mg of the catalyst from Comparative Example 29 were introduced into a glass microreactor placed in an oven at 200 ° C. The catalyst bed is contacted at 200 ° C. with a stream of helium containing 1.6 × 10 ³ Pa of 1,1′-biphenyl and 6 × 10 ⁴ Pa of propylene. The total flow rate of the gaseous mixture is 36 ml / min,
And biphenyl W. H. S. V. The (weight hourly space velocity) is 1.2 g of biphenyl / hour / g of catalyst. 7
Gas chromatographic analysis of the reaction mixture after 0 minutes shows a conversion of 1.6% and a yield of monoisopropylbiphenyl of 1.6%. Diisopropylbiphenyl is not detected.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number in the agency FI Technical display location C07C 15/14 8619-4H 15/24 8619-4H 41/30 43/275 8619-4H // C07B 61/00 300 (72) Inventor Giorzyu Marie Giosef Riyuk Poncelet Belgium 1030 Briyutzell. Avuenra Teini 145 (72) Inventor Maru Joseph Henri Remi Belgium 1348 Le Vuen-la-Neuve. Lieut 41 (72) Inventor Pierre Huernan Marcel Guislen Lardinois Belgium 6559 Robe. Liyudeu Virajyu 46 (72) Inventor Marina Jijan Madeleine Juan Fouquet Belgium 1160 Briyutsusel. Ave Nuda Niel Boon 55

Claims (17)

[Claims] 1. A catalyst of Si / Al of at least 10: 1.
Aroma by reacting an aromatic hydrocarbon with an alkylating agent in the presence of a zeolite catalyst, thereby resulting in an alkyl-substituted derivative, characterized in that it is the acid form of dealuminized small pore mordenite having an atomic ratio. Method for the selective alkylation of group hydrocarbons. 2. The mordenite catalyst is 20: 1 to 100.
Si / Al atomic ratio of 0: 1, symmetry index of 0.7 to 2.6,
0.05-0.12 per gram of catalyst calculated on dry catalyst
A process according to claim 1 in the form of rod-shaped agglomerates having a biphenyl sorption capacity of g and a ratio of medium to macropore volume to total pore volume of 0.2 to 0.5. 3. The catalyst comprises Si / A of 80: 1 to 120: 1.
The method of claim 2 having a 1 atomic ratio. 4. The process according to claim 1, wherein the catalyst is prepared by dealuminizing small pore mordenite by one or more combined hydrothermal and acid treatments. 5. A catalyst from small pore sodium mordenite in the following successive steps: (a) exchange of sodium ions with ammonium ions or protons, (b) heat treatment in the presence of steam, and (c) treatment with aqueous acid solution. The method according to any one of claims 1 to 4, which is produced by a process comprising 6. The aromatic hydrocarbon has the formula I (Ar ¹ -X-A
r ² ) _n -Ar ³ (I) [in the formula, Ar ¹ , Ar ² and A
r ³ may independently of each other represent an unsubstituted or substituted monocyclic or fused or non-fused polycyclic aromatic group, Ar ³ may also represent hydrogen, X is absent or It may represent an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a C ₁ -C ₄ alkylene group, n may be 0 or 1, and when n is 0, A
r ³ is different from hydrogen and (Ar ¹ -X-Ar ² ) _n is hydrogen] is a monocyclic or polycyclic aromatic hydrocarbon having the method according to any one of claims 1 to 5. 7. In the aromatic hydrocarbon of formula I, Ar ¹
And Ar ² are both phenyl, and Ar ³ is phenyl, naphthyl or hydrogen, and naphthyl and each phenyl group are independently halogen, hydroxy group, C ₁ -C ₆
Alkoxy, carboxy, C ₁ -C ₄ carboxyalkyl, or optionally halogen, hydroxy, C ₁ -C substituted by carboxy or C ₁ -C ₆ alkoxy group
₁₂ alkyl groups may be substituted by 1 or 2 groups, X is absent or an oxygen atom, and n is 0 or 1, and when n is 0, Ar ³ is hydrogen. different and ^{(Ar 1 -X-Ar 2)} n the method of claim 6 wherein the hydrogen. 8. The aromatic hydrocarbon of formula I is biphenyl, p
-Terphenyl, diphenyl ether, naphthalene or ethylbenzene, preferably biphenyl.
The method described. 9. The alkylating agent is a C _{2 to} C ₂₀ alkene, C ₂
To C ₂₀ polyolefin, C _{4 to} C ₇ cycloalkene, C ₁
To C ₂₀ alkanol, C _{1 to} C ₂₀ alkyl halide or C _{1 to} C ₂₀ alkyl aromatic hydrocarbon.
9. The method according to claim 8. 10. The alkylating agent is a C _{2 to} C ₆ alkene, C
₁ -C ₆ alkyl halide or C ₁ -C ₆ alkanol, preferably a method according to claim 9, wherein propene or 2-propanol. 11. The method according to claim 1, wherein the biphenyl is dialkylated with propylene. 12. The catalyst has a Cmcm as measured by X-ray diffraction.
12. A method according to any one of claims 1 to 11, further characterized by a crystal structure which comprises most of the region of symmetry and is substantially free of regions of Cmmm symmetry. 13. A process for the alkylation of aromatic hydrocarbons, wherein the Si / Al atomic ratio is from 20: 1 to 1000: 1,
Symmetry index of 0.7-2.6, calculated as 1 with dry catalyst
Use of the acid form of dealuminated small pore mordenite having a biphenyl sorption capacity of 0.05 to 0.12 g per gram and medium and macropore volumes for a total pore volume of 0.2 to 0.5. 14. The use according to claim 13, wherein the dealumination is carried out by one or more combined hydrothermal and acid treatments. 15. The catalyst is Si / 80: 1 to 120: 1.
Having an Al atomic ratio, the aromatic hydrocarbon is ethylbenzene,
Biphenyl, p-terphenyl, naphthalene, or diph
Is an ethyl ether and the alkylating agent is C₂~ C₂₀Al
Ken, C₁~ C ₂₀Alkyl aromatic hydrocarbon, C₁~ C₂₀A
Rutile halide or C₁~ C₂₀Is an alkanol
Use according to any one of claims 13 or 14. 16. The aromatic hydrocarbon is biphenyl,
The use according to claim 15, wherein the alkylating agent is propylene or 2-propanol. 17. The mordenite according to claim 13, further characterized by a crystal structure comprising a majority of the Cmcm symmetric region as measured by X-ray diffraction and substantially free of the Cmmm symmetric region. Use as described in section.